2) United States Patent oy oy cy 3) en @y (86) @ 6s) G0) Jun, 13, 2014 oy Boualleg et al CATALYST WITH A MESOPOROUS AND MACROPOROUS CO-MIXED NICKEI ACTIVE PHASE HAVING A MEDIAN MACROPORE DIAMETER OF MORE THAN 300 NM, AND ITS USE IN HYDROGENATION Applicant: IFP Energies nouvelles, Rueil-Malmaison (FR) Inventors: Malika Boualleg, Villeurbanne (ER) Anne-Claire Dubreuil, Lyons (FR) Emily Maille, Lyons (FR); Cecile ‘Thomazeau, Lyons (FR) Assignee: IFP Energies nouvelles, Rueil-Malmaison (FR) Notice: Subject to any disclaimer, the term ofthis patent is extended or adjusted under 35 USC. 154) by 79 days. Appl. Nos 15/8611 PCT Filed: Jun. 9, 2015 PCT No, § 371 (XI), (2) Date: POTEP2015/062817 Dee. 13, 2016 PCT Pub, Nos WO2015/189191 PCT Pub, Date: Dee. 17, 2015 Prior Publication Data S 201710120224 Al May 4, 2017 Foreign Application Priority Data cs) 14 55430 Int. Bois 2104 BOLD 237755 Bo1s 35/10 BOL 3700 Bol 3702 BOL 3703 Bors 3704 oud 3708 BOL 3716 core $03 core 310 BOL 3720 Bol 33/00 core 30s C106 $5236 C106 45148 C106 4540 C106 45/52 BOL 3500 fe (2006.01) (2006.01) (2005.01), (2006.01) (2005.01), (2006.01) (2005.01), (2006.01) (2006.01) (2008.01) (2005.01), (2006.01) (2005.01), (2006.01) (2005.01) (2006.01) (2006.01) (2006.01) (2006.01), fad BOLI 23/785 (2013.01): BOLI 21704 (013.01): Boxy $¥00 (2013.01) BOLT 35/006 2013.01); BOLS 38/108 (201301): 'US010258969B: US 10,258,969 B2 Apr. 16, 2019 2 (10) Patent No.: (4s) Date of Patent: BOLd 35/1014 (2013.01), BOL 45/1019 (2013.01, BOLI 350038 201301); BOAT 38/1042 (2013.01); BOLT 38/1087 (2013.0); ‘BOLT 35/1061 (2013.01), BOLJ 35/1066 (2013.01), Bony 38/1071 2013.01): Boy 37/009 (201301): BOLT 37/0236 (2013.01) BOLE 37/03 (2013.01), BOLT 377036 (2013.01); Bony 37/04 (2013.01); BOLI 3708 (2013.01); Bory 37716 (2013.01); OLS 3720 (201301): CU7C $703 (2013.01), CO7E 05 (201301): C7C $710 (2013.01). C100 4536, (2013.01); C10 45140 (2013.01); COG 45/48 (2013.01); C10G 4582 (2013.01), COPE 2521/04 (2013.01): CO7C 2523/755 (2013.01) (CUTC 2601/14 (2017.08), C106 2300/1096 (2013.01); C106 2300705 (2013.01) sation Search 68) ld of Cla None See application file for complete search history 66) References Cited US. PATENT DOCUMENTS. 4301057 A NI9SL Sancher Bow 208 264142 AR1.265 A 121985 Ouusjans ea (Coutinved) FOREIGN PATENT DOCUMENTS Ep oiesoo1 AL 1986 Wo 2msorsion AL ‘5/2005 (OTHER PUBLICATIONS Intemational Search Report dated Sep. 9, 2018 fase in come sponng PCTTED2OLSO62817, 4 pages Colin W. Slifka Millen, White, Zelano Primary Examiner (74) Attornes, Agent, or Firm and Branigan, PC on ABSTRACT Te invention concems a catalyst comprising a calcined oxide matrix which is mainly alumina and an active phase comprising nickel, said active phase being at least partially ‘co-mixed within suid ealeined oxide matrix which is lumina, the nickel content being inthe range 5% to 6 ‘weight of said element with respect to the total mass of catalyst, said aetive phase not comprising metal from eroup VIB, the nickel particles having a diameter of less than 15 ‘im, Said eatalyst having a median mesopore diameter i the ‘ange 8 nm 0 25 nm, a median macropore diameter of more than 300 nm, mesopore volume, measured by mercury porosimetry of 30 mL/s or more and total pore volume, measured by mereury porosimetry, of 034 mL/g or more The invention also concems the process for the preparation of sad catalyst, and its use in a hydrogenation process 13 Claims, No Dra ingsUS 10,258,969 B2 Page 2 66) References Cited USS. PATENT DOCUMENTS. 4920089 4 * 41990. Van Beck Bo1s2004 2083 1/1995 Bala ta ‘2001 Sao y 7003 Ginesta et aoosbio14so AL $2005. Aekerman ota * cited by examinerUS 10,258,969 B2 1 (CATALYST WITH A MESOPOROUS AND -MACROPOROUS CO-MIXED NICKEL ACTIVE PHASE HAVING A MEDIAN MACROPORE DIAMETER OF MORE. THAN 300 NM, AND ITS USE IN HYDROGENATION FIELD OF THE INVENTION The invention relates toa co-mixed catalyst with a nickel sctive phase having a texture and formulation which are Javourable to hydrogenation reactions, in particular to eae- tions for the selective hydrogenation of polyunsaturated ‘compounds, or for the hydrogenation of aromaties. The invention also relates to the process forthe preparation of sai catalyst, and to its use in hydrogenation reactions The most active conventional catalysts in hydrogenatos reactions are based on noble metals such as palladium of platinum. These catalysts are used industrially in refining and in petrochemicals for the purification of certain oil euts by hydrogenation, in particular in eactions for the selective 2 hydrogenation of polyunsaturated molecules such as diole- fins, aeetylenes or alkenylaromaties, or in reactions for the hydrogenation of aromatics. Palladium has often heen sub- stituted by nickel, a metal which is less active than palla- «dium and whieh thus has to be used in larger quantities nthe. > ‘catalyst. Thus, niekel-based catalysts generally have a metal ‘content of between 5% and 60% by weight of nickel with respect to the catalyst “The rate of the hydrogenation reaction is governed by several exiteria, sueh as the diffusion of reagents to the surface of the catalyst (external difsional imitations), the diffusion of reagents into the pores of the support towards, the active sites (internal diflusional limitations) and the intrinsic properties of the active pase, such as the size ofthe mtalic particles and the distribution of the active phase within the suppor. ‘Regarding the intemal diffusional limitations, i is impor: tant that the pore distribution of the macropores and mes- ‘opares are adapted t the desired reaction in onder to ensire 99%, Chromanorm, HPLC), the autoclave was close, purge then pressurized to 35 bar (3.5 MPs) with hydrogen and hated to the test temperature of 30° C. At ime 1-0, approximately 30g of @ Inixtue containing sirens, isoprene. msheptane, pense ‘ethil and thiophene wes intwwced ito theautclave. The reaction mixture then had the composition described above fn string was commenced at 1600 ep. The presire the autoclave was kept constant at 35 bar (3.5 MPa} with the aid ofa reserve bot locate upstean ofthe reactor “The pogress ofthe reaction was monitored by analyzing samples fom the reetion mem t regu tme ineeas the syrene was hydgenatod to ethylbenzene withovt Iydtogenation ofthe aromatic ring, and the foprene was bydrogenatod to methylbutene. IF the reaction was pro- longed longer than necessary. the metbylbutencs wereUS 10,258,969 B2 2 ‘ur hydrogenated into isopentane. The hydrogen consump- tion was also monitored with time by the reduetion of pressure in a reserve bot located upstream of the reactor ‘The catalytic setivity was expressed in moles of H, con- sumed per minute and per gram of Ni ‘The catalytic activities measured for catalysts A,B, Cand are reported in Table 2 below. They are with espoct to the catalytic activity measured for eatalyst A (Avro). TABLE 2 Compan of petra nse Ryda ‘entre cana sen ao! Ayn Mote ot Sate of ition » ‘unin of An Cast eon _preinoe reins Aw th)“ This clearly demonstrates the ‘catalyst A prepared in accordance with the invention. Prep ration by co-mixing alumina means tha erystallites of NiO ‘can be obtained which are smaller, and thus the catalytic performances are improved (compared with catalyst C). In ‘contrast, preparation by co-mixing of bochnite (catalyst B) results in major reduction in the eataltic performances because of the presence of big erytallites of NiO and refractory phases (of the nickel aluminate type) formed ‘during high temperature calcining. Adding the speci porosity properties (in terms of the median diameter of the resopores, the median diameter ofthe maeropores andthe ‘macropore volume) 10 the alumina gel used 10 prepare the ‘catalyst in aocordance with the invention is ilustrated by ‘compatison with catalyst D. Example 7: Evaluation of Catalytic Properties of| Catalysts A, B, C and D in the Hydrogenation of “Toluene Catalysts A, B, Cand D described in the above examples ‘were also tested as regards the Toluene hydrogenation neae> “The selective hydrogenation reaction was operated ia the same autoclave as that dseribed for Example 6. Prior to introducing it into the autoclave, a quantity of 2 rm of catalyst was reluced ex situ ina stream of hydrogen ‘of 1 Lihig of catalyst, at 400° C. for 16 hours (temperature ramp-up 1° CJmin), then it was trnsferred into the auto- clave with the exchosion of air. After adding 216 ml of n-heptane (supplier VWR&, purity >99%, Chromanorm. HPLC, the autoclave was closed, purged, then pressurized to 35 bar (5 MPa) of hydrogen and heated to the test temperature of 80° C. AT time 1-0, approximately 26 ¢ of toluene (supplier SDSiP, purity >99 8%) was introduced into the autoclave (te initial composition ofthe resetion mixture was this: toluene 6% by weightin-heptane, 949% by weizht) nd siring was commenced at 1600 rpm. The pressure was kept constant at 35 bar (3.5 MPa) inthe autoclave with the sid ofa reserve bottle located upstream of the reator. "The progress af the reaction was monitored by testing snalyring samples ffom the reaction medium at regular time Jnervals: the toluene was completely hydrogenated to me rove performances of > 0 2 yleyclohexane. The hydrogen consumption was aso moni- tored with time by the reduction of pressure in a reserve bottle Tocated upstream ofthe resetor. The catalytic aetvity ‘was expressed in moles of H consumed per minute and per agram of Ni ‘The catalytic activities measured for catalysts A, B, Cand D are reported in Table 2. They are with respect to the catalytic activity measured for catalyst A (Ayr). Ica be seen that the performances of eatalyst A prepared in accor dance with the invention were improved “The invention claimed is L.A catalyst comprising a ealeined oxide matrix having alumina content ofa east 90% by weight with respect tothe total Weight of the matrix and an setive phase comprising nickel, said active phase being at least partially co-mixed Within sad calcined oxide matrix a nickel content of 5% to {65% by weight with respect fo the total mass of eatalyst, said ‘active phase not comprising metal from group VIB, the nickel inthe form of panieles having a diameter of less than 15 nm, sid catalyst having a median mesopore diameter in the range § nm 40 25 nm, a median macropore diameter of 390 to 800 nm, 2 mesopore volume, measured by mercury porosimety. af 030 mLlg of more, a total pore volume, reasured hy mercury ponsimetry, of 0.44 mL/g or more, and a macropore volume of 20% to 35% of the total pore volume, and wherein the active phase is entirely co-mixed with the calcined oxide mati. 2. The catalyst as claimed in claim 4, in whieh the nickel content is inthe range 10% to 34Yby weight of sid element ‘with respect tothe fotal mass of catalyst 3. The catalyst os claimed in claim 1, having no micropo- “4. The catalyst as claimed in claim 1, ia which the nickel particles have a diameter i the range 1.5 12 8, The catalyst as claimed in claim 1, in which a portion of the active phase is impregnsted onto the calcined oxide 6. Aprocess for the preparation ofa catalyst as claimed in claim 1, comprising: '8) dissolving an acidic aluminium precursor that is ahi miniam sulphate, aluminium chloride oF alussinins nitrate in water, aa temperature of 20°C. 10 90° a pH of 05 to 5, for a period of 2 to 60 minutes, ») adjusting the pH by adding a least one basic precursor that is sodium aluminate, potssium aluminate, ammo- nia, sodium hydroxide or potassium hytroxide to the suspension obtained in), ata temperature of 20°C. 10 50° C., and a pH of 710 10, for'@ period of 5 10 30, minutes, ©) co-precipitation of the suspension obtained from b) by ‘adding to the suspension at least one basic precursor that is sodium aluminate, potssium aluminate, ammo- nia, sodium hydroxide or potassium hydroxide and Teast one acidie precursor that is aluminium sulpht aluminium ehloide, aluminium nitrate, sulphuric acid, hydrochlorie ac ornitrie sci atleast one of the basic ‘or acidic precursors comprising aluminium, the relative flow rate of the acidic and basic precursors being selected in a manner so as a obiin a pH of the reaction medium of 7 t 10 and the flow rate of the acidic and basic precursors containing aluminium being adjusted ina manner so as to obtain a final concentration of alumina in the suspension of 10 to 38 g/L, 4) fikation of the suspension obtained from the 60 ‘precipitation e) in order o obiain an alumina gel, drying ssid lumina gel obtained ind) in order to obtain 1 powder,US 10,258,969 B2 23 1) heat treatment of the powder obtained from e) at a temperature of 500? C. to 1000” C., in the optional presence of a stream of air containing up to 60% by {Volume of water, for # period of 2 o 10 hours, inorder to obtain a caleined porous aluminium oxide, 1) mixing the ealeined porous aluminium oxide obtained from 1) with a solution comprising atleast one nickel precursor in onde to obtain 8 past, 2p shaping the paste obtained, 5) drying the shaped paste at a temperature of 15° C. 10 Jess than 250°C, in order to obtain a dried catalyst, {) optionally. a heat treatment of the dried catalyst at 2 temperature of 250° C. to 1000° C. in the optional presence of water 7. The process as claimed in claims 6, in which al least one recetion treatment k) is earied out in the presence of @ reducing gas aller i) or j) in onler to obtain a catalyst ‘comprising nickel which i at least partially ia the metalic orm, '8. The process as claimed in elsim 7, in which a pass vation 1) using a sulphur-cootsining or oxygen-containing ‘compound or CO. is caried out before orale the reduction treatment 9. The process as claimed in claim 6, in which the ‘concentration of alumina in the suspension of alumina gel ‘obtained in e) is 13 0 35 g/t 10. The process as claimed in claim 6, in which the acidic precursor of a) and ¢) is aluminium sulphate, aluminium 2 chloride of slunsiniu nitrate, and ia which the basic pre- cursor of a) and ¢) is sodium aluminate or potassium aluminate 11. A hydrogenation process, in which the catalyst as 5 claimed in claim 1 is brought into contact, in the presence of | bylogen, with a feed of hydrocarbons containing palyan- saturated molecules andor aromatic molecules in a manner sueh as o oblai an at least partially hydrogenated elven. 12, The hydrogenation process as claimed in claim 11, in a selective hydrogenation i carried out at a tempera ture of °C. to 500” C., at a pressure of 0.1 10 20 MPa, at ‘mola ratio of hydrogen/(polyunsaturated compounds to be hydrogenated) of 0.1 to 10 and at an hourly space velocity (f 0.1 to 200 h for liguid feed, of 100 to 15000 for 8 gaseous feed, of a hydmearhon feed containing palyan- saturated compounds containing at last 2 carbon atoms per ‘molecule and having a final boiling point of 250° C. or Iss. 13, The hydrogenation process as claimed in claim 11, in 4 hydrogenation of aromatics is curried out at a temperature of 30°C, to 350° C., ata pressure of .1 10 20 MPa, ata molar ratio of hydrogen (aromatic compounds t0 be hydrogenated) of 0.1 to 10 and at an hourly space velocity of 0.05 to SO hr of a feed of hydrocarbons containing 2 aromatic componnds and having a inal boiling point of 650" Corless